WO2017010389A1

WO2017010389A1 - Polyamide resin fiber, production method for polyamide resin fiber, polyamide resin composition, woven fabric, and knitted fabric

Info

Publication number: WO2017010389A1
Application number: PCT/JP2016/070080
Authority: WO
Inventors: 浩介大塚; 加藤　智則
Original assignee: 三菱瓦斯化学株式会社
Priority date: 2015-07-16
Filing date: 2016-07-07
Publication date: 2017-01-19
Also published as: CN107735514B; RU2017144019A3; KR101872002B1; JPWO2017010389A1; EP3323914B1; KR20170108159A; RU2017144019A; CN107735514A; EP3323914A4; US20180171142A1; EP3323914A1; TW201708391A; CA2978918A1; CA2978918C; TWI604013B; JP6164379B2

Abstract

Provided are a polyamide resin fiber having an excellent durability, a production method for the polyamide resin fiber, a polyamide resin composition, and a woven fabric. The polyamide resin fiber contains 0.5-15 parts by weight of a compound represented by general formula (1) relative to 100 parts by weight of a polyamide resin, which is formed from diamine-derived structural units and dicarboxylic acid-derived structural units, wherein at least 50 mol% of the diamine-derived structural units are derived from xylylenediamine, and at least 50 mol% of the dicarboxylic acid-derived structural units are derived from a C4-20 α,ω-linear aliphatic dicarboxylic acid. (In general formula (1), R¹ represents a C1-10 alkyl group, R² represents a C2-12 alkyl group, and n is an integer from 1 to 3.)

Description

Polyamide resin fiber, method for producing polyamide resin fiber, polyamide resin composition, woven fabric and knitted fabric

The present invention relates to a polyamide resin fiber, a method for producing a polyamide resin fiber, a polyamide resin composition, a woven fabric and a knitted fabric.

Polyamide resin is a resin excellent in heat resistance and mechanical strength, and has various applications.
For example, in Patent Document 1, (A) 5 to 90 parts by weight of a polyphenylene ether-based resin and (B) 95 to 10 parts by weight of a polyamide resin are combined with 100 parts by weight of (C) a compatibilizing agent 0.01 A thermoplastic resin composition comprising: 30 parts by weight, (D) 0.1 to 100 parts by weight of a plasticizer that imparts flexibility to polyamide, and (E) 0 to 100 parts by weight of a rubber-like substance. It is disclosed. Further, Patent Document 1 describes that such a thermoplastic resin composition has flexibility and high tensile strength at the same time. Patent Document 1 describes that such a thermoplastic resin composition is used for pipes and tubes.
On the other hand, Patent Document 2 describes a hollow structure comprising a layer made of a resin composition comprising one or more semi-aromatic polyamides and one or more functional polyolefins. ing. Such hollow structures are described to exhibit a balance of properties regarding flexibility, permeability barrier to refrigerant fluid, and retention of properties upon heating and exposure to refrigerant fluid.
Further, in Patent Document 3, (A) 2 to 60 parts by weight of a compound represented by the general formula (1) with respect to 100 parts by weight of a polyamide resin selected from polyamide 11, polyamide 12 or a mixture thereof,

(In the formula, m is an integer of 7 or more and 10 or less.)
(B) A polyamide resin composition comprising 0.05 to 5 parts by weight of a monohydric alcohol having 16 to 24 carbon atoms having a branched chain is disclosed. Examples of applications of such polyamide resin compositions include industrial robots, construction machines, fuel hoses for automobiles, hydraulic and pneumatic tubes, and injection molded parts for automobile interiors.

Japanese Patent Application Laid-Open No. 07-157651 International Publication WO2011 / 084421 Pamphlet JP 7-11131 A

As described above, the polyamide resin is processed into various shapes. Furthermore, in recent years, polyamide resin fibers in which a polyamide resin or a polyamide resin composition is made into a fiber form are also used. Among such polyamide resin fibers, xylylenediamine-based polyamide resin fibers are useful because of their low water absorption and excellent chemical resistance. However, since the polyamide resin fibers are fibers, high durability is particularly required as compared with polyamide resin molded products having other shapes.
The object of the present invention is to provide a polyamide resin fiber having excellent durability. Moreover, it aims at providing the manufacturing method of a polyamide resin fiber, a polyamide resin composition, a textile fabric, and knitting.

As a result of investigations by the present inventors based on the above problems, it has been found that the above problems can be solved by the following means. Specifically, the above problem has been solved by the following means.
<1> 0.5 to 15 parts by weight of the compound represented by the general formula (1) with respect to 100 parts by weight of the polyamide resin,
The polyamide resin is composed of a structural unit derived from a diamine and a structural unit derived from a dicarboxylic acid,
50 mol% or more of the structural unit derived from diamine is derived from xylylenediamine, and 50 mol% or more of the structural unit derived from dicarboxylic acid is an α, ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms. Polyamide resin fiber derived from
General formula (1)

In the general formula (1), R ¹ is an alkyl group having 1 to 10 carbon atoms, R ² is an alkyl group having 2 to 12 carbon atoms, and n is an integer of 1 to 3.
<2> The polyamide resin fiber according to <1>, wherein the fineness of the polyamide resin fiber is 50 to 800 dtex.
<3> The polyamide when the polyamide resin fiber is fixed and the ceramic plate derived from aluminum oxide is brought into contact with the polyamide resin fiber while rotating a ceramic plate derived from aluminum oxide at a friction plate rotation speed of 120 rpm so that an average load of 150 g is applied. The polyamide resin fiber according to <2>, wherein the number of rotations until the resin fiber is cut is 100 or more.
<4> The polyamide resin fiber according to any one of <1> to <3>, wherein the xylylenediamine comprises 30 to 100 mol% metaxylylenediamine and 0 to 70 mol% paraxylylenediamine.
<5> The polyamide resin fiber according to any one of <1> to <4>, wherein 50 mol% or more of the structural units derived from the dicarboxylic acid are derived from at least one of sebacic acid and adipic acid.
<6> The polyamide resin fiber according to any one of <1> to <4>, wherein 50 mol% or more of the structural units derived from the dicarboxylic acid are derived from adipic acid.
<7> The polyamide resin fiber according to any one of <1> to <6>, wherein a phosphorus atom concentration in the polyamide resin fiber is 0.1 to 10 ppm.
<8> The polyamide resin fiber according to any one of <1> to <7>, wherein the tensile strength measured according to JIS L 1013 is 2.0 cN / dtex or more.
<9> The polyamide resin fiber according to any one of <1> to <8>, wherein the polyamide resin fiber is stretched.
<10> 0.5 to 15 parts by weight of the compound represented by the general formula (1) with respect to 100 parts by weight of the polyamide resin, and the polyamide resin is composed of a structural unit derived from a diamine and a structural unit derived from a dicarboxylic acid. 50 mol% or more of the structural unit derived from the diamine is derived from xylylenediamine, and 50 mol% or more of the structural unit derived from the dicarboxylic acid is an α, ω-linear aliphatic having 4 to 20 carbon atoms. A process for producing a polyamide resin fiber, comprising drawing a fiber comprising a polyamide resin composition derived from dicarboxylic acid;
General formula (1)

In the general formula (1), R ¹ is an alkyl group having 1 to 10 carbon atoms, R ² is an alkyl group having 2 to 12 carbon atoms, and n is an integer of 1 to 3.
<11> The method for producing a polyamide resin fiber according to <10>, wherein the stretching is performed in two or more stages.
<12> The method for producing a polyamide resin fiber according to <10> or <11>, wherein the overall draw ratio is 4.1 times or more.
<13> The method for producing a polyamide resin fiber according to any one of <10> to <12>, wherein the fiber before stretching has a fineness of 100 to 5000 dtex.
<14> 0.5 to 15 parts by weight of the compound represented by the general formula (1) with respect to 100 parts by weight of the polyamide resin, and the polyamide resin is composed of a structural unit derived from a diamine and a structural unit derived from a dicarboxylic acid. 50 mol% or more of the structural unit derived from the diamine is derived from xylylenediamine, and 50 mol% or more of the structural unit derived from the dicarboxylic acid is an α, ω-linear aliphatic having 4 to 20 carbon atoms. A polyamide resin composition derived from a dicarboxylic acid;
General formula (1)

In the general formula (1), R ¹ is an alkyl group having 1 to 10 carbon atoms, R ² is an alkyl group having 2 to 12 carbon atoms, and n is an integer of 1 to 3.
<15> The polyamide resin composition according to <14>, wherein a phosphorus atom concentration in the polyamide resin composition is 0.1 to 10 ppm.
<16> The polyamide resin composition according to <14> or <15>, which is used for producing a stretched polyamide resin fiber.
<17> A woven fabric using the fiber according to any one of <1> to <9>.
<18> A knitted fabric using the fiber according to any one of <1> to <9>.

According to the present invention, it has become possible to provide a polyamide resin fiber excellent in durability, a method for producing a polyamide resin fiber, a polyamide resin composition, a woven fabric and a knitted fabric.

It is the schematic which shows the manufacturing process of the polyamide resin fiber of this invention.

Hereinafter, the contents of the present invention will be described in detail. In this specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value. In this specification, ppm means weight ppm.

The polyamide resin fiber of the present invention contains 0.5 to 15 parts by weight of the compound represented by the general formula (1) with respect to 100 parts by weight of the polyamide resin, and the polyamide resin is derived from a diamine-derived structural unit and a dicarboxylic acid. 50 mol% or more of the structural unit derived from diamine is derived from xylylenediamine, and 50 mol% or more of the structural unit derived from dicarboxylic acid is α, ω having 4 to 20 carbon atoms. -Derived from linear aliphatic dicarboxylic acids.
General formula (1)

In the general formula (1), R ¹ is an alkyl group having 1 to 10 carbon atoms, R ² is an alkyl group having 2 to 12 carbon atoms, and n is an integer of 1 to 3.
By setting it as such a structure, the polyamide resin fiber excellent in durability is obtained.

The blending of a plasticizer such as a compound represented by the general formula (1) with a polyamide resin is described in Patent Document 1, Patent Document 2, and Patent Document 3, for example. However, when the present inventor examined, it was composed of a structural unit derived from a diamine and a structural unit derived from a dicarboxylic acid, and 50 mol% or more of the structural unit derived from the diamine was derived from xylylenediamine, and derived from the dicarboxylic acid. A polyamide resin in which 50 mol% or more of the structural unit is derived from an α, ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms (hereinafter sometimes referred to as “XD polyamide resin”) has a general formula ( By blending the compound represented by 1) at a predetermined ratio, it was possible to achieve remarkably excellent durability.
That is, when a plasticizer is added, the crystallization temperature of the polyamide resin at the time of temperature rise generally tends to decrease. When the crystallization temperature is lowered, crystallization is likely to proceed, and stretching is usually difficult. Here, also when the compound represented by the general formula (1) was blended with the XD-based polyamide resin, the crystallization temperature at the time of the temperature rise decreased. However, despite the decrease in the crystallization temperature at the time of temperature rise, fibers made of a polyamide resin composition comprising a combination of an XD-based polyamide resin and a compound represented by the general formula (1) can be easily drawn. Met. Furthermore, in the case of the fiber which consists of a polyamide resin composition, it discovered that a draw ratio could be raised compared with the case where the compound represented by General formula (1) is not added. Furthermore, as a result of the polyamide resin fiber of the present invention being drawn at a high draw ratio, it has achieved excellent mechanical strength (tensile strength and strength at the time of cutting). In particular, as will be described later, this is surprising because it is a phenomenon that does not occur even when other plasticizers are blended. Furthermore, since the polyamide resin fiber of the present invention contains a compound represented by the general formula (1), which is a kind of plasticizer, it has a high draw ratio and a synergistic effect of plasticizing effect by the plasticizer. A polyamide resin fiber excellent in abrasion is obtained. Based on the above, the present invention has succeeded in providing a polyamide resin fiber capable of achieving durability.
Details of the present invention will be described below.

The polyamide resin fiber of the present invention comprises a polyamide resin composition containing 0.5 to 15 parts by weight of the compound represented by the general formula (1) with respect to 100 parts by weight of the XD polyamide resin. More preferably, it is formed by stretching a fiber made of the polyamide resin composition. Hereinafter, the details of the polyamide resin composition of the present invention will be described.

<XD polyamide resin>
The XD-based polyamide resin used as an essential component in the present invention is composed of a structural unit derived from a diamine and a structural unit derived from a dicarboxylic acid, and 50 mol% or more of the structural unit derived from the diamine is derived from xylylenediamine, More than 50 mol% of the structural unit derived from the acid is derived from the α, ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms.

The XD-based polyamide resin is preferably derived from at least one mol of xylylenediamine, more preferably at least 70 mol%, more preferably at least 80 mol%, more preferably at least 90 mol% of the structural unit derived from diamine. Preferably at least 70 mol%, more preferably at least 80 mol%, particularly preferably at least 90 mol% of the structural units, and at least one of α, ω-linear aliphatic dicarboxylic acids having 4 to 20 carbon atoms are preferred. It is preferably derived from the seed.

The diamine component that is the raw material of the XD-based polyamide resin contains 70% by mole or more of metaxylylenediamine, more preferably 80% by mole or more, and still more preferably 90% by mole or more. When the metaxylylenediamine in the diamine component is 70 mol% or more, the polyamide resin obtained therefrom can exhibit excellent gas barrier properties.
More specifically, the xylylenediamine is preferably composed of 30 to 100 mol% metaxylylenediamine and 0 to 70 mol% paraxylylenediamine, and preferably 70 to 100 mol% metaxylylenediamine and 0. More preferably, it consists of ˜30 mol% paraxylylenediamine.

Examples of diamines other than xylylenediamine that can be used as the raw material diamine component of the XD polyamide resin include tetramethylenediamine, pentamethylenediamine, 2-methylpentanediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, and nonamethylene. Aliphatic diamines such as diamine, decamethylenediamine, dodecamethylenediamine, 2,2,4-trimethyl-hexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 1,3-bis (aminomethyl) cyclohexane, 1 , 4-bis (aminomethyl) cyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, bis (4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propyl Aliphatic diamines such as bread, bis (aminomethyl) decalin, bis (aminomethyl) tricyclodecane, diamines having aromatic rings such as bis (4-aminophenyl) ether, paraphenylenediamine, bis (aminomethyl) naphthalene Etc., and one kind or a mixture of two or more kinds can be used.
When a diamine other than xylylenediamine is used as the diamine component, it is used in an amount of 30 mol% or less, preferably 1 to 25 mol%, particularly preferably 5 to 20 mol% of the structural unit derived from the diamine.

The α, ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms that is preferably used as the raw material dicarboxylic acid component of the XD-based polyamide resin includes α, ω-linear aliphatic dicarboxylic acid having 6 to 16 carbon atoms. Α, ω-linear aliphatic dicarboxylic acid having 6 to 10 carbon atoms is more preferable. Examples of the α, ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms include succinic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, adipic acid, sebacic acid, undecanedioic acid, and dodecanedioic acid. Aliphatic dicarboxylic acids can be exemplified, and one or more can be mixed and used, but among these, the melting point of the polyamide resin is in an appropriate range for molding, so at least one of adipic acid and sebacic acid One is preferred, and adipic acid is particularly preferred.

Examples of the dicarboxylic acid component other than the α, ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms include phthalic acid compounds such as isophthalic acid, terephthalic acid and orthophthalic acid, 1,2-naphthalenedicarboxylic acid, 3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 1,7-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3- Examples thereof include naphthalenedicarboxylic acids such as isomers such as naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and 2,7-naphthalenedicarboxylic acid, and one kind or a mixture of two or more kinds can be used.

When a dicarboxylic acid other than an α, ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms is used as the dicarboxylic acid component, terephthalic acid or isophthalic acid may be used from the viewpoint of molding processability and barrier properties. preferable. The proportion of terephthalic acid and isophthalic acid is preferably 30 mol% or less, more preferably 1 to 30 mol%, particularly preferably 5 to 20 mol% of the structural unit derived from dicarboxylic acid.

Here, “consisting of a structural unit derived from a diamine and a structural unit derived from a dicarboxylic acid” means that the amide bond constituting the XD-based polyamide resin is formed by a bond between the dicarboxylic acid and the diamine. Moreover, XD type polyamide resin contains other site | parts, such as a terminal group, in addition to the structural unit derived from dicarboxylic acid and the structural unit derived from diamine. Furthermore, there may be a case where a repeating unit having an amide bond that is not derived from a bond between a dicarboxylic acid and a diamine, a trace amount of impurities, and the like are included. Specifically, the XD polyamide resin is a component constituting the polyamide resin in addition to the diamine component and the dicarboxylic acid component, and lactams such as ε-caprolactam and laurolactam, aminocapron as long as the effects of the present invention are not impaired. Aliphatic aminocarboxylic acids such as acids and aminoundecanoic acids can also be used as copolymerization components. In the present invention, 90% by weight or more of the XD polyamide resin is preferably a structural unit derived from diamine or a structural unit derived from dicarboxylic acid.

The XD polyamide resin used in the present invention preferably has a phosphorus atom concentration of 0.1 to 10 ppm, more preferably 1 to 8 ppm. By setting it as such a range, the improvement of continuous productivity by prevention of yellowing of a fiber and suppression of clogging of a polymer filter is compatible, and the effect of the present invention is more effectively exhibited.
As will be described later, the polyamide resin fibers used in the present invention preferably have a phosphorus atom concentration in a predetermined range, but such phosphorus atoms are usually derived from a polyamide resin.

The XD polyamide resin used in the present invention preferably has a number average molecular weight (Mn) of 6,000 to 30,000, more preferably 8,000 to 28,000, still more preferably 9,000 to 26,000. When it is in such a range, the moldability becomes better.

The number average molecular weight (Mn) referred to here is the following formula based on the terminal amino group concentration [NH ₂ ] (μ equivalent / g) and the terminal carboxyl group concentration [COOH] (μ equivalent / g) of the polyamide resin. Calculated.
Number average molecular weight (Mn) = 2,000,000 / ([COOH] + [NH ₂ ])

The XD polyamide resin used in the present invention preferably has a molecular weight distribution (weight average molecular weight / number average molecular weight (Mw / Mn)) of 1.8 to 3.1. The molecular weight distribution is more preferably 1.9 to 3.0, still more preferably 2.0 to 2.9. By setting the molecular weight distribution in such a range, a composite material having excellent mechanical properties tends to be easily obtained.
The molecular weight distribution of the XD polyamide resin can be adjusted, for example, by appropriately selecting the polymerization reaction conditions such as the type and amount of the initiator and catalyst used during the polymerization, and the reaction temperature, pressure, and time. It can also be adjusted by mixing a plurality of types of XD polyamide resins having different average molecular weights obtained under different polymerization conditions or by separately precipitating the polymerized XD polyamide resins.

The molecular weight distribution can be obtained by GPC measurement. Specifically, using “HLC-8320GPC” manufactured by Tosoh Corporation as an apparatus and two “TSK gel Super HM-H” manufactured by Tosoh Corporation as a column, eluent Measured under conditions of hexafluoroisopropanol (HFIP) having a sodium trifluoroacetate concentration of 10 mmol / l, a resin concentration of 0.02% by weight, a column temperature of 40 ° C., a flow rate of 0.3 ml / min, and a refractive index detector (RI). It can obtain | require as a value of polymethylmethacrylate conversion. A calibration curve is prepared by dissolving 6 levels of PMMA in HFIP.

The XD polyamide resin has a terminal amino group concentration ([NH ₂ ]) of preferably less than 100 μequivalent / g, more preferably 5 to 75 μequivalent / g, and still more preferably 10 to 60 μequivalent / g. The carboxyl group concentration ([COOH]) is preferably less than 150 μeq / g, more preferably 10 to 120 μeq / g, and still more preferably 10 to 100 μeq / g. By using the XD-based polyamide resin having such a terminal group concentration, the viscosity is easily stabilized when the XD-based polyamide resin is processed into a film or fiber, and the reactivity with a carbodiimide compound described later is good. Tend to be.

Further, the ratio of the terminal amino group concentration to the terminal carboxyl group concentration ([NH ₂ ] / [COOH]) is preferably 0.7 or less, more preferably 0.6 or less, particularly preferably 0. .5 or less. When this ratio is larger than 0.7, it may be difficult to control the molecular weight when polymerizing the XD polyamide resin.

The terminal amino group concentration can be measured by dissolving 0.5 g of XD polyamide resin in 30 ml of a phenol / methanol (4: 1) mixed solution with stirring at 20-30 ° C. and titrating with 0.01 N hydrochloric acid. . The terminal carboxyl group concentration was determined by dissolving 0.1 g of XD polyamide resin in 30 ml of benzyl alcohol at 190 ° C., cooling in a 40 ° C. water bath, and titrating 0.01 N (normative) KOH solution. Can be measured.
The description of paragraphs 0052 to 0053 of JP-A-2014-173196 can be referred to for the production method of the XD polyamide resin, and the contents thereof are incorporated in the present specification.

In the present invention, the melting point of the XD polyamide resin is preferably 150 to 350 ° C., more preferably 180 to 300 ° C., and still more preferably 180 to 250 ° C.
Further, the glass transition point of the XD polyamide resin is preferably 50 to 100 ° C., more preferably 55 to 100 ° C., and particularly preferably 60 to 100 ° C. Within this range, the heat resistance tends to be good.

The melting point in the present invention is the temperature at the peak top of the endothermic peak at the time of temperature rise observed by the DSC (Differential Scanning Calorimetry) method. Specifically, it is measured by the method described in the examples described later. Value. When the equipment used in the examples is not available due to reasons such as out of print, it can be measured using other equipment having equivalent performance. Hereinafter, the same applies to other measurement methods.
The glass transition point refers to a glass transition point that is measured by once heating and melting a sample to eliminate the influence of the thermal history on crystallinity and then raising the temperature again. For the measurement, for example, “DSC-60” manufactured by Shimadzu Corporation is used, the sample amount is about 1 mg, nitrogen is flowed at 30 ml / min as the atmospheric gas, and the heating rate is 10 ° C./min. The polyamide resin heated and melted from room temperature to a temperature higher than the expected melting point under dry conditions is rapidly cooled with dry ice, and the temperature is raised again to a temperature higher than the melting point at a rate of 10 ° C./min to obtain the glass transition point. Can do.

Further, the lower limit of the crystallization temperature at the time of temperature rise of the XD polyamide resin is preferably 50 ° C. or higher, more preferably 80 ° C. or higher, further preferably 100 ° C. or higher, particularly preferably 120 ° C. or higher, and 140 ° C. or higher. Even more preferred. Further, the upper limit of the crystallization temperature of the XD polyamide resin at the time of temperature rise is preferably 180 ° C. or less, more preferably 170 ° C. or less, further preferably 162 ° C. or less, particularly preferably 155 ° C. or less, and preferably 148 ° C. or less. Even more preferred.
Further, the XD-based polyamide resin used in the present invention is a compound in which the crystallization temperature at the time of temperature rise when the compound represented by 5% by weight of the general formula (1) is blended is represented by the general formula (1) Is preferably lower than the crystallization temperature at the time of temperature rise when not blended, the difference is more preferably 3 ° C. or more, further preferably 5 ° C. or more, and preferably 10 ° C. or more. Particularly preferred. The upper limit of the difference in crystallization temperature at the time of temperature rise is not particularly defined, but can be, for example, 40 ° C. or lower, further 35 ° C. or lower, and particularly 30 ° C. or lower. it can.
The measuring method of the crystallization temperature at the time of temperature rising in this invention follows the method as described in the Example mentioned later.

The proportion of the XD polyamide resin in the polyamide resin composition of the present invention is 50% by weight or more, preferably 60% by weight or more, more preferably 70% by weight or more, and 80% by weight or more. You can also.

<Other polyamide resins>
The polyamide resin composition of the present invention may contain a polyamide resin other than the XD polyamide resin. Examples of such other polyamide resins include polyamide 4, polyamide 6, polyamide 11, polyamide 12, polyamide 46, polyamide 66, polyamide 610, polyamide 612, polyhexamethylene terephthalamide (polyamide 6T), polyhexamethylene isophthalate. Examples include ramid (polyamide 6I), polyamide 66 / 6T, polyamide 9T, polyamide 9MT, polyamide 6I / 6T, and the like. Among these, when other polyamide resins are included, at least one of polyamide 6 and polyamide 66 is preferable.
The content of the other polyamide resin in the polyamide resin composition of the present invention is preferably 1 to 50 parts by weight, more preferably 5 to 40 parts by weight, based on 100 parts by weight of the XD polyamide resin.

<Compound represented by the general formula (1)>
The polyamide resin composition of this invention contains the compound represented by General formula (1).

In the general formula (1), R ¹ is an alkyl group having 1 to 10 carbon atoms, R ² is an alkyl group having 2 to 12 carbon atoms, and n is an integer of 1 to 3.

In the compound represented by the general formula (1), it is presumed that the OH group part improves the familiarity with the XD polyamide resin. The OH group moiety may be substituted at any of the ortho, para and meta positions, but the para position is more preferred.
In the compound represented by the general formula (1), the group represented by — (CH ₂ ) _n — is presumed to play the role of a linking group that connects the hydroxyphenyl ester group and —CR ¹ R ^2. . n is preferably 1 or 2, and more preferably 1.

In the compound represented by the general formula (1), —CR ¹ R ² is presumed to play a role as a site for increasing the compatibility with the XD polyamide resin.
In the compound represented by the general formula (1), R ¹ is preferably an alkyl group having 1 to 9 carbon atoms, more preferably an alkyl group having 2 to 9 carbon atoms, and 2 to 8 carbon atoms. The alkyl group is more preferably an alkyl group having 3 to 7 carbon atoms, particularly preferably an alkyl group having 4 to 6 carbon atoms. The alkyl group as R ¹ is preferably a linear or branched alkyl group, and more preferably a linear alkyl group.
In the compound represented by the general formula (1), R ² is preferably an alkyl group having 2 to 10 carbon atoms, more preferably an alkyl group having 3 to 9 carbon atoms, and 5 to 9 carbon atoms. Are more preferable, and an alkyl group having 6 to 8 carbon atoms is particularly preferable. The alkyl group as R ² is preferably a linear or branched alkyl group, and more preferably a linear alkyl group.
In the present invention, in the compound represented by the general formula (1), the number of carbon atoms constituting R ² is preferably 2 or more, and preferably 2 to 4 larger than the number of carbon atoms constituting R ^1. More preferred. By adopting such a configuration, the effect of the present invention is more effectively exhibited.

Below, the example of a compound represented by General formula (1) is given. However, it goes without saying that the present invention is not limited to these examples.

The compound represented by the general formula (1) contains 0.5 to 15 parts by weight of the compound represented by the general formula (1) with respect to 100 parts by weight of the polyamide resin in the polyamide resin composition. The lower limit of the compound represented by the general formula (1) is 0.5 parts by weight or more, preferably 0.6 parts by weight or more, more preferably 0.8 parts by weight or more, and 1.0 part by weight or more. Is more preferable, and 2.0 parts by weight or more is particularly preferable. The upper limit is 15 parts by weight or less, preferably 10 parts by weight or less, more preferably 8 parts by weight or less, and further preferably 7 parts by weight or less.
Only 1 type may be sufficient as the compound represented by General formula (1), and 2 or more types may be sufficient as it. When 2 or more types are included, the total amount is preferably within the above range.
Further, when the compound represented by the general formula (1) is blended in an amount of preferably 8 to 15 parts by weight, more preferably 9 to 13 parts by weight, based on 100 parts by weight of the polyamide resin, the melt viscosity can be lowered. More specifically, the polyamide resin composition containing the compound represented by the general formula (1) at the above ratio has a melt viscosity of 500 Pa · s at 260 ° C. and an apparent shear rate of 122 (S ⁻¹ ). It can be: The lower limit value of the melt viscosity in this case is not particularly defined, but can be set to, for example, 400 Pa · s or more. Furthermore, the temperature at which the weight is increased at a rate of 10 ° C./min and the weight is reduced by 3% by weight with respect to the weight at 150 ° C. of the polyamide resin composition containing the compound represented by the general formula (1) at the above ratio. Can be high. In particular, these effects are remarkable as compared with the case where a plasticizer other than the compound represented by the general formula (1) is blended.
Only 1 type may be sufficient as the compound represented by General formula (1), and 2 or more types may be sufficient as it. When 2 or more types are included, the total amount is preferably within the above range.

The polyamide resin composition of the present invention may contain one or more plasticizers other than the compound represented by the general formula (1). Examples of such other plasticizers include the plasticizers described in paragraph 0039 of JP-A No. 7-11131, the contents of which are incorporated herein. However, the polyamide resin composition of the present invention preferably has a configuration that does not substantially contain a plasticizer other than the compound represented by the general formula (1). “Substantially free” means that, for example, in the polyamide resin composition of the present invention, the content of the other plasticizer is 0.1% by weight or less of the weight of the compound represented by the general formula (1). Say.

<Other resin components>
The polyamide resin composition of the present invention may contain a resin component other than the polyamide resin. Other resin components other than polyamide resins include polyolefin resins such as polyethylene and polypropylene, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polycarbonate resins, polyoxymethylene resins, polyether ketones, polyether sulfones, and thermoplastic polyethers. A thermoplastic resin such as imide is exemplified.
In addition, the polyamide resin composition of the present invention can be configured to contain substantially no thermoplastic resin other than the polyamide resin. “Substantially not contained” means that, for example, in the polyamide resin composition of the present invention, the content of the thermoplastic resin other than the polyamide resin is 5% by weight or less of the weight of the polyamide resin.

<Other additives>
Further, the polyamide resin composition of the present invention includes an antioxidant, a stabilizer such as a heat stabilizer, a hydrolysis resistance improver, a weather resistance stabilizer, and a matting agent as long as the objects and effects of the present invention are not impaired. Additives such as ultraviolet absorbers, nucleating agents, plasticizers, dispersants, flame retardants, antistatic agents, anti-coloring agents, anti-gelling agents, coloring agents, release agents, and the like can be added. Details of these can be referred to the description of paragraphs 0130 to 0155 of Japanese Patent No. 4894982, the contents of which are incorporated herein.
However, the polyamide resin composition is an XD polyamide resin and the compound represented by the general formula (1), and preferably accounts for 80% by weight or more, more preferably 90% by weight or more.
Moreover, although the polyamide resin composition of this invention may contain fillers, such as carbon fiber, it is preferable not to contain substantially. “Substantially free” means, for example, that the blending amount of the filler is 3% by weight or less of the polyamide resin composition of the present invention.
As described above, the polyamide resin composition of the present invention is preferably used for the production of polyamide resin fibers, and more preferably for the production of stretched polyamide resin fibers. Moreover, you may use for another use.

The melting point of the polyamide resin composition of the present invention is preferably 150 to 350 ° C., more preferably 180 to 300 ° C., and further preferably 180 to 250 ° C.
Further, the lower limit of the crystallization temperature at the time of heating of the polyamide resin composition of the present invention is preferably 50 ° C. or higher, more preferably 80 ° C. or higher, further preferably 100 ° C. or higher, particularly preferably 120 ° C. or higher, 140 It can also be set to ° C or lower. Moreover, the upper limit of the crystallization temperature at the time of temperature rising of the polyamide resin composition of the present invention is preferably 180 ° C. or less, more preferably 170 ° C. or less, further preferably 162 ° C. or less, particularly preferably 155 ° C. or less. It is even more preferable that the temperature is not higher than ° C.
Furthermore, the polyamide resin composition used in the present invention is a compound in which the crystallization temperature at the time of temperature rise when the compound represented by 5% by weight of the general formula (1) is blended is represented by the general formula (1) Is preferably lower than the crystallization temperature at the time of temperature rise when not blended, the difference is more preferably 3 ° C. or more, further preferably 5 ° C. or more, and preferably 10 ° C. or more. Particularly preferred. The upper limit of the difference in crystallization temperature at the time of temperature rise is not particularly defined, but can be, for example, 40 ° C. or lower, further 35 ° C. or lower, and particularly 30 ° C. or lower. it can.

Characteristics of Polyamide Resin Fiber The polyamide resin fiber of the present invention fixes the polyamide resin fiber to the polyamide resin fiber while rotating the ceramic plate derived from aluminum oxide at a friction plate rotation speed of 120 rpm so that an average load of 150 g is applied. A polyamide resin fiber having a rotation speed (hereinafter sometimes referred to as “abrasion-resistant rotation speed”) of 100 or more until the polyamide resin fiber is cut when brought into contact with each other can be obtained. Such high wear resistance is achieved by blending the XD polyamide resin with the compound represented by the general formula (1) and stretching.
For example, the rotational speed of the abrasion resistance can be measured by passing the fiber to be measured through each yarn guide, fixing both ends of the fiber with a terminal and a clip carrying an arbitrary load, holding a recording pen over the fiber, and turning on the switch to turn the friction disc. Measured as the number of revolutions until the fiber breaks, using a device that is loaded on a friction piece, which is a ceramic plate derived from 11 differently shaped aluminum oxides attached to the friction disc . As a testing machine for performing such a test, FIG. 1 on page 564 of a conjugation force testing machine (textile engineering, Vol. 26, No. 7 1973) manufactured by Hiruta Riken Co., LTD. Examples of the described yarn-bonding force tester). More specifically, the wear-resistant rotational speed in the present invention is a value measured by the method described in the examples.
Since the polyamide resin fiber of the present invention can be drawn at a high draw ratio and contains a compound (plasticizer) represented by the general formula (1), high wear resistance can be achieved. The wear-resistant rotational speed in the present invention is preferably 100 or more. The upper limit of the wear-resistant rotational speed is not particularly defined and is preferably higher. For example, when a polyamide resin in which 50 mol% or more of the structural unit derived from dicarboxylic acid is derived from adipic acid is used, even if it is 250 or less, it is practically used. , Excellent level. Moreover, when using the polyamide resin from which 50 mol% or more of structural units derived from dicarboxylic acid derive from sebacic acid, even if it is 1500 or less, it is a practically excellent level.

Further, the polyamide resin fiber of the present invention can have a tensile strength measured according to JIS L 1013 of 2.0 cN / dtex or more, and further 2.2 cN / dtex or more. The upper limit of the tensile strength is not particularly defined and is preferably higher. For example, when a polyamide resin in which 50 mol% or more of the structural units derived from dicarboxylic acid are derived from adipic acid is used, 4.0 cN / dtex. Even below, it is a practically excellent level. Moreover, when using the polyamide resin from which 50 mol% or more of structural units derived from dicarboxylic acid derive from sebacic acid, even if it is 8.0 cN / dtex or less, it is a practically excellent level.

The phosphorus atom concentration of the polyamide resin fiber of the present invention is preferably 0.1 to 10 ppm, and more preferably 1 to 8 ppm. By setting it as such a range, the prevention of yellowing of a fiber and the improvement of continuous productivity are compatible, and the effect of this invention is exhibited more effectively. Here, the phosphorus component contained in the polyamide resin fiber includes a phosphorus component derived from a polyamide resin, a phosphorus component derived from various additives (for example, a flame retardant), and the like.

The length (weight average fiber length) of the polyamide resin fiber of the present invention is not particularly defined, but is usually 2 cm or more, preferably in the range of 0.1 m to 20,000 m, more preferably 1 m to It is 10,000 m, more preferably 100 m to 7,000 m.

The lower limit of the fineness of the polyamide resin fiber of the present invention is preferably 50 dtex or more, more preferably 60 dtex or more, further preferably 70 dtex or more, particularly preferably 80 dtex or more, and 110 dtex. The above is more preferable. The upper limit value is preferably 10,000 dtex or less, more preferably 1000 dtex or less, further preferably 800 dtex or less, and particularly preferably 600 dtex or less. Such a polyamide resin fiber may be a monofilament, but is usually a multifilament composed of two or more monofilaments. When the polyamide resin fiber in the present invention is a multifilament, the number of fibers is preferably 10 to 1000 f, more preferably 10 to 500 f, and further preferably 20 to 100 f.
In particular, 60 dtex to 120 dtex is preferable for apparel use. For example, 100 to 1500 dtex is preferable for use for fishing nets, and 1000 to 3000 dtex is preferable for use for tire cords.

The cross section of the polyamide resin fiber of the present invention is usually circular. The term “circular” as used herein includes not only a circular in the mathematical sense, but also includes those that are generally recognized as circular in the technical field of the present invention. Moreover, the cross section of the polyamide resin fiber in the present invention may be a shape other than a circle, and may be a flat shape such as an ellipse or an oval, for example.

Next, an embodiment in which the polyamide resin fiber in the present invention is a multifilament will be described. It goes without saying that the present invention is not limited to these forms. As will be described in detail later, a step of forming monofilament polyamide resin fibers into a bundle may be included in the course of the production steps of the polyamide resin fibers of the present invention.
As the first embodiment of the multifilament in the present invention, polyamide resin fibers are bundled with at least one of a sizing agent and a surface treatment agent (sometimes referred to as oil agent, sizing agent, etc.). It is done. In this case, the sizing agent and the surface treatment agent are not particularly limited as long as they have a function of converging polyamide resin fibers, but are not limited to oil agents such as mineral oil and animal / vegetable oil, and nonionic surfactants. And surfactants such as anionic surfactants and amphoteric surfactants. More specifically, ester compounds, alkylene glycol compounds, polyolefin compounds, phenyl ether compounds, polyether compounds, silicone compounds, polyethylene glycol compounds, amide compounds, sulfonate compounds, phosphate compounds, A carboxylate compound and a combination of two or more of these are preferred.
The total amount of the sizing agent and the surface treating agent for the polyamide resin fiber is preferably 0.1 to 5.0% by weight, more preferably 0.5 to 2.0% by weight, based on the polyamide resin fiber.
The treatment method of the polyamide resin fiber with the sizing agent and / or the surface treatment agent is not particularly defined as long as the intended purpose can be achieved. For example, a sizing agent and / or a surface treatment agent dissolved in a solution is added to a polyamide resin fiber, and the sizing agent and / or the surface treatment agent is attached to the surface of the polyamide resin fiber. Alternatively, the sizing agent and / or the surface treatment agent can be air blown to the surface of the polyamide resin fiber.

The second embodiment of the multifilament in the present invention is exemplified by a method of twisting into a bundle. When twisting, only the polyamide resin fibers may be twisted, or other resin fibers or fibers other than resin fibers may be twisted together. Examples of fibers other than resin fibers include carbon fibers. The twist is preferably applied after stretching, and further after stretching and heat setting.
In addition to twisting, as described in the first embodiment of the multifilament, means for treating with a sizing agent, a surface treatment agent, or the like may be used in combination.
The method of twisting is not particularly defined, and a known method can be adopted. The number of twists can be appropriately determined according to the number of fibers of the polyamide resin fiber, the fineness, and the like. For example, it can be 1 to 200 times / m (fiber length), and more preferably 1 to 100 times / m. More preferably, it can be 1 to 70 times / m, and particularly 1 to 50 times / m.

The third embodiment of the multifilament in the present invention is exemplified by a core-sheath structure. The core-sheath structure refers to, for example, a form consisting of two or more regions, such as a pencil core and a sheath. In the present invention, a monofilament or multifilament polyamide resin fiber is used as a core, and the periphery thereof is formed. It is preferable to provide a layer structure that serves as a sheath. By setting it as such a structure, the characteristic of a polyamide resin fiber can be changed and it becomes possible to use it for many kinds of uses.
The core and sheath portions do not have to be completely distinguished as regions. For example, when the core portion is a multifilament composed of a plurality of polyamide resin fibers, a part of the material constituting the sheath may penetrate between the polyamide resin fibers constituting the multifilament.
Further, the core portion may be made of only polyamide resin fibers or may contain other fibers. Further, the core portion may be the multifilament of the first embodiment or the second embodiment.
On the other hand, the sheath portion can be appropriately determined according to the application. For example, when an adhesive is used for the sheath portion, it preferably serves as an adhesive when a nonwoven fabric or the like is produced using such multifilaments. As an adhesive used for the sheath portion, for example, a resin composition having a melting point lower than that of the core polyamide resin fiber, for example, a polyamide resin (MXD6) for the core and a polypropylene resin (PP) for the sheath, the sheath is heated by heating. Preferably serves as an adhesive.

Method for Producing Polyamide Resin Fiber The method for producing a polyamide resin fiber of the present invention comprises 0.5 to 15 parts by weight of the compound represented by the general formula (1) with respect to 100 parts by weight of the polyamide resin, It is composed of a structural unit derived from diamine and a structural unit derived from dicarboxylic acid, 50 mol% or more of the structural unit derived from diamine is derived from xylylenediamine, and 50 mol% or more of the structural unit derived from dicarboxylic acid is carbon. The method comprises drawing a fiber comprising a polyamide resin composition derived from an α, ω-linear aliphatic dicarboxylic acid having 4 to 20 atoms. By setting it as such a structure, the polyamide resin fiber excellent in durability is obtained. Moreover, since the manufacturing method of the polyamide resin fiber of this invention is excellent in durability, even if it produces continuously, it is hard to cut | disconnect a fiber, It becomes a manufacturing method excellent in continuous production (especially continuous production of 100 m or more). Here, the said polyamide resin (XD type polyamide resin) and the compound represented by General formula (1) are synonymous with the above-mentioned, and a preferable range is also the same.
The polyamide resin fiber is usually produced according to a melt spinning method. As an example of a method for producing a polyamide resin fiber, a step of melt spinning a polyamide resin composition, a step of passing a fiber comprising a polyamide resin composition after melt spinning through a cooling zone, and drawing a fiber comprising a polyamide resin composition The method including the process to do is mentioned.
Moreover, the process which makes the fiber which consists of the polyamide resin composition which carried out the melt spinning pass the hot zone may be included before the process which passes a cooling zone. And a step of applying a sizing agent and / or a surface treating agent to the fibers of the polyamide resin composition before the step of drawing the fibers of the polyamide resin composition after the step of passing through the cooling zone. You may go out. In addition, after the stretching step, a step of heat-setting a fiber made of the polyamide resin composition may be included. Furthermore, after heat setting, the process which twists the fiber which consists of a polyamide resin composition may be included.
Hereinafter, although the manufacturing method of the polyamide resin fiber of this invention is demonstrated concretely according to FIG. 1, the manufacturing method of this invention is not limited to this.

That is, a polyamide resin composition containing an XD-based polyamide resin, a compound represented by the general formula (1), other additives, and the like is melted and discharged from a die (1 in FIG. 1). The temperature at which the nozzle 1 is discharged is defined as the spinning temperature.
At this time, the number of holes in the base may be one, or two or more. For example, when manufacturing a multifilament, it is preferable to provide the number of holes according to the number of fibers. As an example, a base having 10 to 100 holes is exemplified. The lower limit of the temperature (spinning temperature) of the polyamide resin composition at the time of discharge is preferably a temperature equal to or higher than the melting point of the XD-based polyamide resin, more preferably the melting point of the XD-based polyamide resin + 5 ° C or higher. More preferable is a melting point of + 10 ° C. or higher. Although the upper limit of the temperature of the polyamide resin composition at the time of discharge is not particularly defined, it can be, for example, the melting point of the XD polyamide resin + 60 ° C. or lower. When two or more kinds of XD polyamide resins are included, the temperature of the XD polyamide resin at the time of discharge may be set based on the melting point of the XD polyamide resin having the lowest melting point. In addition, when the XD polyamide resin has two or more melting points, the temperature may be set based on the lowest melting point.
The fiber composed of the spun polyamide resin composition usually passes through a hot zone and a cooling zone. When the molten polyamide resin composition passes through the die, the polyamide resin composition is oriented. The hot zone plays a role of relaxing the orientation of the polyamide resin composition, and is usually a region having a length of about several tens of centimeters. The cooling zone plays a role of cooling the fiber made of the polyamide resin composition to such an extent that it can be stretched. Usually, cold air is blown to the polyamide resin composition in a region having a length of about several meters. The cooling air in the cooling zone is preferably in the range of 10 to 100 ° C. and 10 to 50 m / min. The temperature of the fiber that has passed through the cooling zone is preferably about room temperature (eg, 10 to 40 ° C.).

Fibers made from the spun polyamide resin composition can be bundled. As a method for forming a bundle, the first and second embodiments of the multifilament described above are preferable. For example, as shown in FIG. 1, a bundling agent and / or a surface treatment agent may be added to form a bundle. As a means for adding the sizing agent and / or the surface treatment agent, in FIG. 1, the sizing agent is immersed in the solution 2 containing the sizing agent and / or the surface treatment agent, but other means may be used. Of course, the polyamide resin fiber to be produced may be a monofilament, and in this case, such a step is unnecessary.

The fiber made of the melt-spun polyamide resin composition is preferably stretched. Stretching may be performed by stretching a fiber made of a melt-spun polyamide resin composition as it is, or may be stretched in a bundled state, but is usually stretched in a bundled state. The stretching may be one-stage stretching or two-stage or more stretching, preferably two-stage stretching, preferably 2 to 4 stage stretching, and more preferably 2 or 3 stage stretching.
When extending | stretching in two steps or more, it is preferable to make the draw ratio of extending | stretching of the 2nd step or higher sequentially higher than the 1st step | stretching. The stretching ratio of the first stretching is preferably 1.03 or more, more preferably 1.03 to 3.0, and even more preferably 1.03 to 2.0, although it depends on the application. The draw ratio of the second drawing is preferably 1.5 to 10.0 times, more preferably 2.0 to 6.0 times, and even more preferably 2.5 to 5.0 times. This embodiment is particularly preferable when a polyamide resin in which 50 mol% or more of the structural units derived from dicarboxylic acid are derived from adipic acid is used.
As another embodiment, when stretching in two or more stages, the stretching ratio of stretching in the second and subsequent stages can be sequentially reduced as compared with stretching in the first stage. In this case, the draw ratio of the first drawing is preferably 1.5 to 10.0 times, more preferably 2.0 to 6.0 times, and even more preferably 2.5 to 5.0 times. The stretching ratio of the second stretching is preferably 1.03 or more, more preferably 1.03 to 3.0, and even more preferably 1.03 to 2.0, although it depends on the application. This embodiment is particularly preferable when a polyamide resin in which 50 mol% or more of the structural units derived from dicarboxylic acid are derived from sebacic acid is used.
In addition, when manufacturing using a roll, for example, even between the PR roll and GR1 in FIG. 1, a slight difference in peripheral speed occurs between the rolls, and some stretching (for example, a stretch of less than 1.06, May stretch less than 1.03 times).
The stretching is preferably performed by using two rolls (stretching rolls) having different peripheral speeds of the rolls. The ratio of the peripheral speeds of the two rolls is the draw ratio. That is, the draw ratio between the two rolls is expressed as the peripheral speed of the roll through which the fiber passes / the peripheral speed of the roll through which the fiber passes first. In FIG. 1, after spinning, the film is slightly stretched (stretched) between the roll PR and the roll GR1, the first stretching is performed between the roll GR1 and the roll GR2, and the second stretching is performed between the roll GR2 and the roll GR3. Is going. That is, the roll GR1 has a higher peripheral speed of the roll than the roll PR, the roll GR2 has a higher peripheral speed of the roll than the roll GR1, and the roll GR3 has a higher peripheral speed of the roll than the roll GR2. .
In the present invention, the lower limit of the total draw ratio of the fibers made of the polyamide resin composition is preferably 1.5 times or more, more preferably 4.1 times or more, and 4.2 times or more. It is particularly preferred that it is 4.5 times or more, more preferably 5.0 times or more. The upper limit value is more preferably 15 times or less, further preferably 10 times or less, particularly preferably 8 times or less, and further preferably 5.5 times or less. Here, the total draw ratio refers to the product of the draw ratios.
When stretching using a roll, the total stretching ratio can be calculated from the following formula.
Total draw ratio (times) = roll speed A / roll speed B
The roll speed A is the speed of the roll through which the fiber finally passes among the drawn rolls, and the roll speed B is the speed of the roll through which the fiber passes first among the drawn rolls.

In stretching, heating may be performed, and heating is preferable. Heating is preferably performed by adjusting the surface temperature of the roll. About the surface temperature of a roll, it can set suitably according to the kind of XD type polyamide resin, a desired draw ratio, etc. For example, in the example of FIG. 1, the surface temperature of the roll GR1 is the melting point of the XD-based polyamide resin − (180 to 130 ° C.), the surface temperature of the roll GR2 is the surface temperature of the roll GR1 + (5 to 25 ° C.), The surface temperature of the roll GR3 can be set to the surface temperature of the roll GR2 + (26 to 100) ° C.
Depending on the type of plasticizer, the plasticizer may volatilize and adhere to the roll during manufacture of the polyamide resin fiber, making it difficult to stretch. However, when a compound represented by the general formula (1) is used, There is no such problem.

The fineness of the fiber before drawing (fineness of the bundled fiber) is preferably 50 to 10,000 dtex, more preferably 100 to 8000 dtex, further preferably 100 to 5000 dtex, and 200 to 4000 dtex. Is more preferable, and 300 to 3000 dtex is even more preferable. When the fibers before stretching are multifilaments, the number of fibers is preferably 10 to 1000 f, more preferably 10 to 500 f, and further preferably 20 to 100 f. *

In the method for producing a polyamide resin fiber of the present invention, relaxation may be performed after stretching. The relaxation can be performed, for example, between the roll GR3 and the roll GR4 and between the roll GR4 and the roll WD in FIG. That is, it is preferable to relax between two rolls (relaxation rolls) having different peripheral speeds.
The relaxation rate can be calculated from the following formula when relaxing using a roll, for example, and is preferably 1 to 10%, more preferably 2 to 5%.
Relaxation rate (%) = {1− (roll speed C / roll speed D)} × 100
Roll speed C refers to the roll speed of the roll through which the fibers pass last among the relaxing rolls, and roll speed D refers to the roll speed of the roll through which the fibers first pass among the relaxing rolls. The relaxation roll through which the fiber first passes is generally a drawing roll through which the fiber passes last. That is, one roll may serve as both a relaxation roll and a stretching roll.
Regarding the surface temperature of the roll during relaxation, for example, in the example shown in the figure, the surface temperature of the roll GR4 can be set to the surface temperature of the roll GR3− (20 to 80) ° C.

The relaxed polyamide resin fiber is usually wound and stored on a roll or the like. Moreover, the obtained polyamide resin fiber can be cut and used in various applications.
The final draw ratio after relaxation of the polyamide resin fiber of the present invention is preferably 4.0 times or more, more preferably 4.2 times or more, and even 5.0 or more. Good. Moreover, although the upper limit of the final draw ratio is not particularly defined, it can be, for example, 6.0 times or less.
The final draw ratio means the draw ratio of the finally obtained polyamide resin fiber based on the total draw ratio and the relaxation rate compared with before the draw, and is a value calculated from the following formula.
Final draw ratio = (total draw ratio) × {(100−relaxation rate) / 100}

Use of polyamide resin fiber The polyamide resin fiber of the present invention may be used as a fiber as it is, or may be processed into a molding material such as a mixed yarn or a braided string. Further, it is also preferably used as a molding material such as woven fabric, knitted fabric, and non-woven fabric.
These may use only polyamide resin fibers as fiber components, but it is also preferable to use them in combination with other resin fibers or reinforcing fibers. In particular, examples of reinforcing fibers include carbon fibers and glass fibers.
The polyamide resin fiber and molding material of the present invention are used for transport parts such as automobiles, general machine parts, precision machine parts, electronic / electric equipment parts, OA equipment parts, building materials / residential equipment parts, medical devices, leisure sports goods (for example, , Fishing line), play equipment, medical products, food packaging films, clothing and other daily necessities, defense and aerospace products.

The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

<Raw materials>
<< Synthesis of polyamide resin MXD6 >>
After adding 0.3 g of sodium hypophosphite monohydrate and 0.1 g of sodium acetate to 8.9 kg of adipic acid and heating and melting at 170 ° C. at 0.1 MPaA in a reaction can, the contents were stirred. Then, 8.3 kg of metaxylylenediamine was gradually added dropwise over 2 hours to raise the temperature to 250 ° C. After the temperature rise, the pressure was gradually decreased to 0.08 MPaA over 1 hour and held for 0.5 hour. After completion of the reaction, the contents were taken out in a strand shape and pelletized with a pelletizer to obtain 15 kg pellets. The obtained pellets were charged into a tumbler (rotary vacuum tank) having a heating medium heating mantle, and heated at 200 ° C. for 1 hour in a reduced pressure state (0.5 to 10 Torr), thereby solidifying the obtained pellets. Phase polymerization was performed to obtain a polyamide resin (MXD6, melting point: 237 ° C., relative viscosity: 2.65, moisture content: 0.05%).

<< Synthesis of polyamide resin MP10 >>
After adding 0.3 g of sodium hypophosphite monohydrate and 0.1 g of sodium acetate to 10.1 kg of sebacic acid and heating and melting at 170 ° C. at 0.1 MPaA in a reactor, the contents were stirred. While, 6.7 kg of mixed diamine of metaxylylenediamine and paraxylylenediamine (metaxylylenediamine / paraxylylenediamine = 70/30 (% by weight)) was gradually added dropwise over 2 hours, and the temperature was 250 ° C. Was raised. After the temperature rise, the pressure was gradually decreased to 0.08 MPaA over 1 hour and held for 0.5 hour. After completion of the reaction, the contents were taken out in a strand shape and pelletized with a pelletizer to obtain 15 kg pellets. The obtained pellets were placed in a tumbler (rotary vacuum tank) having a heating medium heating mantle, and heated at 195 ° C. for 1 hour in a reduced pressure state (0.5 to 10 Torr). Phase polymerization was performed to obtain a polyamide resin (MP10, melting point: 213 ° C., relative viscosity: 2.60, moisture content: 0.03%).

<< Plasticizer >>
HD-PB: Hexyldecyl p-hydroxybenzoate, manufactured by Kao Corporation, Exepearl HD-PB
EH-PB: ethyl hexyl p-hydroxybenzoate, obtained from Tokyo Chemical Industry Co., Ltd. EH-OB: ethyl hexyl o-hydroxybenzoate, obtained from Tokyo Chemical Industry Co., Ltd. BBSA: N-butylbenzenesulfonamide, Daihachi Chemical Industry Co., Ltd. Company made, BM-4

Example 1
<Production method of polyamide resin fiber>
A polyamide resin composition in which the plasticizer shown in Table 1 was blended in the proportion (unit: parts by weight) shown in Table 1 with respect to 100 parts by weight of the polyamide resin shown in Table 1 was melt-spun according to FIG. Specifically, a polyamide resin composition obtained by melting and kneading each component was prepared by using a spinning temperature of 260 ° C., a discharge rate of 24 g / min, a die width of 0.7 mm, and a die having 48 nozzle holes (the total number of fibers during spinning is Spinning was performed under the conditions of 48f). Fibers made of a polyamide resin composition that has been spun are allowed to pass through a hot zone and a cooling zone, and then fibers made of a polyamide resin composition that has become approximately room temperature (hereinafter sometimes referred to as “fibers before stretching”) are bundled. It was immersed in an agent (Takemoto Yushi Co., Ltd., Delion PP-807) (2 in FIG. 1) to form a bundle. Thereafter, each roll was passed at the roll speed and roll surface temperature shown in Table 1. Here, the roll PR is not heated. In Table 1, the stretch ratio between rolls PR and GR1 is a stretch, the stretch between GR1 and GR2 is a first stretch, and the stretch between GR2 and GR3 is a second stretch. The overall draw ratio is the product of these three draw ratios. Thereafter, relaxation was performed between the rolls GR3 and GR4 and between the rolls GR4 and WD to obtain polyamide resin fibers. The obtained polyamide resin fiber was wound up on a roll.
Various characteristics of the obtained polyamide resin fiber were evaluated. The results are shown in Table 1 below.

<Measurement of crystallization temperature at the time of temperature rise of the fiber before drawing>
DSC-60 manufactured by SHIMADZU CORPORATION is used, the sample amount is 1 mg, nitrogen gas is flowed at 30 ml / min as the atmospheric gas, and the temperature rise rate is expected from room temperature (25 ° C.) at 10 ° C./min. The temperature at the peak top of the exothermic peak observed when heated to a temperature equal to or higher than the melting point is defined as the crystallization temperature when the polyamide resin fiber is heated.

<Difference in crystallization temperature at the time of temperature rise of the fiber before drawing (Δ temperature rise crystallization temperature)>
The difference of the crystallization temperature at the time of temperature rising of the polyamide resin fiber of each Example and a comparative example and the crystallization temperature at the time of temperature rising of the polyamide resin fiber in the comparative example 1 were computed.

<Measurement of melting point of fiber before drawing>
DSC-60 manufactured by SHIMADZU CORPORATION is used, the sample amount is 1 mg, nitrogen gas is flowed at 30 ml / min as the atmospheric gas, and the temperature rise rate is expected from room temperature (25 ° C.) at 10 ° C./min. Of the endothermic peak observed when the molten polyamide resin fiber is rapidly cooled with dry ice and heated again to a temperature above the melting point at a rate of 10 ° C./min. The peak top temperature was defined as the melting point of the polyamide resin fiber.

<Measurement of phosphorus atom concentration of polyamide resin fiber>
0.5 g of polyamide resin fibers were weighed, 20 ml of concentrated sulfuric acid was added, and wet decomposition was performed on a heater. After cooling, 5 ml of hydrogen peroxide was added, heated on a heater, and concentrated until the total amount was 2 to 3 ml. The mixture was cooled again to 500 ml with pure water. Quantification was performed at a wavelength of 213.618 nm by high frequency inductively coupled plasma (ICP) emission analysis using IRIS / IP manufactured by Thermo Jarrel Ash.

<Measurement of fineness>
The fineness (positive fineness) of the polyamide resin fiber was measured in accordance with JIS L 1013: 2010.

<Strength at cutting and tensile strength>
According to JIS L 1013, after adjusting the humidity of the polyamide resin fiber in an environment of 23 ° C. and 50% RH, the load is measured when the polyamide resin fiber is cut by measuring the distance between the chucks at 20 cm and the tensile speed of 20 cm / min. Measured as strength of time. The tensile strength was calculated according to JIS L 1013 by dividing the strength at the time of cutting by the fineness (positive fineness) of the polyamide resin fiber.

<Abrasion resistance test>
A ceramic plate derived from aluminum oxide was manufactured by friction plate rotation speed (Hiruta Riken Co., LTD.), And a conjugation force tester (textile engineering, Vol. 26, No. 7 1973) so that an average load of 150 g was applied. Using a yarn binding force tester described in FIG. 1 on page 564 of the yearly issue), while rotating at 120 rpm, the number of rotations until the polyamide resin fibers were cut was measured.

Example 6
A polyamide resin composition in which the plasticizer shown in Table 1 was blended in the proportion (unit: parts by weight) shown in Table 1 with respect to 100 parts by weight of the polyamide resin shown in Table 1 was melt-spun according to FIG. Specifically, a polyamide resin composition obtained by melt-kneading each component is a spin temperature of 260 ° C., a discharge amount of 5 g / min, a base width of 0.7 mm, a base having 34 holes in the base (the total number of fibers during spinning is Spinning was performed under the conditions of 34f). Fibers made of a polyamide resin composition that has been spun are allowed to pass through a hot zone and a cooling zone, and then fibers made of a polyamide resin composition that has become approximately room temperature (hereinafter sometimes referred to as “fibers before stretching”) are bundled. It was immersed in an agent (Takemoto Yushi Co., Ltd., Delion PP-807) (2 in FIG. 1) to form a bundle. Thereafter, each roll was passed at the roll speed and roll surface temperature shown in Table 1. Here, the roll PR is not heated. In Table 1, the stretch ratio between rolls PR and GR1 is a stretch, the stretch between GR1 and GR2 is a first stretch, and the stretch between GR2 and GR3 is a second stretch. The overall draw ratio is the product of these three draw ratios. Thereafter, relaxation was performed between the rolls GR3 and GR4 and between the rolls GR4 and WD to obtain polyamide resin fibers. The obtained polyamide resin fiber was wound up on a roll.
The obtained polyamide resin fiber was evaluated for various characteristics in the same manner as in Example 1. The results are shown in Table 1 below.

Example 7
A polyamide resin composition in which the plasticizer shown in Table 1 was blended in the proportion (unit: parts by weight) shown in Table 1 with respect to 100 parts by weight of the polyamide resin shown in Table 1 was melt-spun according to FIG. Specifically, a polyamide resin composition obtained by melt-kneading each component is a spin temperature of 260 ° C., a discharge amount of 36 g / min, a base width of 0.7 mm, a base having 72 holes in the base (the total number of fibers during spinning is 72f). Fibers made of a polyamide resin composition that has been spun are allowed to pass through a hot zone and a cooling zone, and then fibers made of a polyamide resin composition that has become approximately room temperature (hereinafter sometimes referred to as “fibers before stretching”) are bundled. It was immersed in an agent (Takemoto Yushi Co., Ltd., Delion PP-807) (2 in FIG. 1) to form a bundle. Thereafter, each roll was passed at the roll speed and roll surface temperature shown in Table 1. Here, the roll PR is not heated. In Table 1, the stretch ratio between rolls PR and GR1 is a stretch, the stretch between GR1 and GR2 is a first stretch, and the stretch between GR2 and GR3 is a second stretch. The overall draw ratio is the product of these three draw ratios. Thereafter, relaxation was performed between the rolls GR3 and GR4 and between the rolls GR4 and WD to obtain polyamide resin fibers. The obtained polyamide resin fiber was wound up on a roll.
The obtained polyamide resin fiber was evaluated for various characteristics in the same manner as in Example 1. The results are shown in Table 1 below.

<Examples 2 to 5, 8 and Comparative Examples 1 to 5>
In Example 1, as shown in Table 1, raw materials and stretching conditions were changed, and the others were performed in the same manner.
The results are shown in Table 1 below.

In the above table, in Comparative Example 2, the fiber made of the polyamide resin composition was cut during stretching. Moreover, in the comparative example 3, the fiber which consists of a polyamide resin composition stuck to the roll at the time of extending | stretching, and it fractured | ruptured. In Comparative Example 4, the fiber made of the polyamide resin composition was broken during stretching. In Comparative Example 5, the fiber made of the polyamide resin composition was cut during the stretching.

<Manufacture of textiles>
The polyamide resin fiber was used for warp and weft and was adjusted with plain weave so that the basis weight was 300 g / m ² . It was confirmed that the fabrics of the examples were excellent in durability.
<Manufacture of knitted fabric>
The polyamide resin fibers were used and adjusted by knitting so that the basis weight was 300 g / m ² . It was confirmed that the knitted fabrics of the examples were excellent in durability.

1 base 2 sizing agent 11 hot zone 12 cooling zone

Claims

Containing 0.5 to 15 parts by weight of the compound represented by the general formula (1) with respect to 100 parts by weight of the polyamide resin;
The polyamide resin is composed of a structural unit derived from a diamine and a structural unit derived from a dicarboxylic acid,
50 mol% or more of the structural unit derived from diamine is derived from xylylenediamine, and 50 mol% or more of the structural unit derived from dicarboxylic acid is an α, ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms. Polyamide resin fiber derived from
General formula (1)

In the general formula (1), R 1 is an alkyl group having 1 to 10 carbon atoms, R 2 is an alkyl group having 2 to 12 carbon atoms, and n is an integer of 1 to 3.
The polyamide resin fiber according to claim 1, wherein the fineness of the polyamide resin fiber is 50 to 800 dtex.
The polyamide resin fiber when the polyamide resin fiber is brought into contact with the polyamide resin fiber while rotating a ceramic plate derived from aluminum oxide at a friction plate rotation speed of 120 rpm so that an average load of 150 g is applied. The polyamide resin fiber according to claim 2, wherein the number of rotations until breaking is 100 or more.
The polyamide resin fiber according to any one of claims 1 to 3, wherein the xylylenediamine comprises 30 to 100 mol% metaxylylenediamine and 0 to 70 mol% paraxylylenediamine.
The polyamide resin fiber according to any one of claims 1 to 4, wherein 50 mol% or more of the structural units derived from the dicarboxylic acid are derived from at least one of sebacic acid and adipic acid.
The polyamide resin fiber according to any one of claims 1 to 4, wherein 50 mol% or more of the structural units derived from the dicarboxylic acid are derived from adipic acid.
The polyamide resin fiber according to any one of claims 1 to 6, wherein a phosphorus atom concentration in the polyamide resin fiber is 0.1 to 10 ppm.
The polyamide resin fiber according to any one of claims 1 to 7, wherein the tensile strength measured according to JIS L 1013 is 2.0 cN / dtex or more.
The polyamide resin fiber according to any one of claims 1 to 8, wherein the polyamide resin fiber is drawn.
Containing 0.5 to 15 parts by weight of the compound represented by the general formula (1) with respect to 100 parts by weight of the polyamide resin;
The polyamide resin is composed of a structural unit derived from a diamine and a structural unit derived from a dicarboxylic acid,
50 mol% or more of the structural unit derived from diamine is derived from xylylenediamine, and 50 mol% or more of the structural unit derived from dicarboxylic acid is an α, ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms. A process for producing a polyamide resin fiber, comprising drawing a fiber comprising a polyamide resin composition derived from
General formula (1)

In the general formula (1), R 1 is an alkyl group having 1 to 10 carbon atoms, R 2 is an alkyl group having 2 to 12 carbon atoms, and n is an integer of 1 to 3.
The manufacturing method of the polyamide resin fiber of Claim 10 which performs the said extending | stretching in two or more steps.
The method for producing a polyamide resin fiber according to claim 10 or 11, wherein the overall draw ratio is 4.1 times or more.
The method for producing a polyamide resin fiber according to any one of claims 10 to 12, wherein the fiber before stretching has a fineness of 100 to 5000 dtex.
Containing 0.5 to 15 parts by weight of the compound represented by the general formula (1) with respect to 100 parts by weight of the polyamide resin;
The polyamide resin is composed of a structural unit derived from a diamine and a structural unit derived from a dicarboxylic acid,
50 mol% or more of the structural unit derived from diamine is derived from xylylenediamine, and 50 mol% or more of the structural unit derived from dicarboxylic acid is an α, ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms. A polyamide resin composition derived from
General formula (1)

In the general formula (1), R 1 is an alkyl group having 1 to 10 carbon atoms, R 2 is an alkyl group having 2 to 12 carbon atoms, and n is an integer of 1 to 3.
The polyamide resin composition according to claim 14, wherein a phosphorus atom concentration in the polyamide resin composition is 0.1 to 10 ppm.
The polyamide resin composition according to claim 14 or 15, which is used for producing a stretched polyamide resin fiber.
A woven fabric using the fiber according to any one of claims 1 to 9.
A knitted fabric using the fiber according to any one of claims 1 to 9.